Substitution Effects in Aryl Halides and Amides into the Reaction Mechanism of Ullmann-Type Coupling Reactions

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dc.article.number1770
dc.catalogadorgjm
dc.contributor.authorDurán, Rocío
dc.contributor.authorBarrales Martínez, César
dc.contributor.authorSantana Romo, Fabián Mauricio
dc.contributor.authorRodríguez Sánchez, Diego Fernando
dc.contributor.authorZacconi, Flavia C. M.
dc.contributor.authorHerrera Pisani, Bárbara Andrea
dc.date.accessioned2024-04-16T14:13:26Z
dc.date.available2024-04-16T14:13:26Z
dc.date.issued2024
dc.description.abstractIn this article, we present a comprehensive computational investigation into the reaction mechanism of N-arylation of substituted aryl halides through Ullmann-type coupling reactions. Our computational findings, obtained through DFT ωB97X-D/6-311G(d,p) and ωB97X-D/LanL2DZ calculations, reveal a direct relation between the previously reported experimental reaction yields and the activation energy of haloarene activation, which constitutes the rate-limiting step in the overall coupling process. A detailed analysis of the reaction mechanism employing the Activation Strain Model indicates that the strain in the substituted iodoanilines is the primary contributor to the energy barrier, representing an average of 80% of the total strain energy. Additional analysis based on conceptual Density Functional Theory (DFT) suggests that the nucleophilicity of the nitrogen in the lactam is directly linked to the activation energies. These results provide valuable insights into the factors influencing energetic barriers and, consequently, reaction yields. These insights enable the rational modification of reactants to optimize the N-arylation process.
dc.fechaingreso.objetodigital2024-04-16
dc.format.extent16 páginas
dc.fuente.origenORCID
dc.identifier.doi10.3390/molecules29081770
dc.identifier.urihttps://doi.org/10.3390/molecules29081770
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/85135
dc.information.autorucEscuela de Química; Santana Romo, Fabián Mauricio; 0000-0002-8753-3349; 1031362
dc.information.autorucEscuela de Química; Rodríguez Sánchez, Diego Fernando; S/I; 1059619
dc.information.autorucEscuela de Química; Zacconi, Flavia C. M.; 0000-0002-3676-0453; 1011127
dc.information.autorucEscuela de Química; Herrera Pisani, Bárbara Andrea; 0000-0003-1911-4473; 4439
dc.issue.numero8
dc.language.isoen
dc.nota.accesocontenido completo
dc.revistaMolecules
dc.rightsacceso abierto
dc.rights.licenseCC BY 4.0 DEED Attribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectComputational chemistry
dc.subjectConceptual DFT
dc.subjectReaction mechanisms
dc.subjectN-arylations
dc.subjectSubstituent effect
dc.titleSubstitution Effects in Aryl Halides and Amides into the Reaction Mechanism of Ullmann-Type Coupling Reactions
dc.typeartículo
dc.volumen29
sipa.codpersvinculados1031362
sipa.codpersvinculados1059619
sipa.codpersvinculados1011127
sipa.codpersvinculados4439
sipa.trazabilidadORCID;2024-04-15
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